CN100543543C - A kind of transmission-type of improvement or reflective liquid-crystal display and preparation method thereof - Google Patents
A kind of transmission-type of improvement or reflective liquid-crystal display and preparation method thereof Download PDFInfo
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- CN100543543C CN100543543C CNB2005100682213A CN200510068221A CN100543543C CN 100543543 C CN100543543 C CN 100543543C CN B2005100682213 A CNB2005100682213 A CN B2005100682213A CN 200510068221 A CN200510068221 A CN 200510068221A CN 100543543 C CN100543543 C CN 100543543C
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- liquid crystal
- miniature cup
- display box
- crystal components
- lcd
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/60—Pleochroic dyes
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1347—Arrangement of liquid crystal layers or cells in which the final condition of one light beam is achieved by the addition of the effects of two or more layers or cells
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/542—Macromolecular compounds
- C09K19/544—Macromolecular compounds as dispersing or encapsulating medium around the liquid crystal
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133377—Cells with plural compartments or having plurality of liquid crystal microcells partitioned by walls, e.g. one microcell per pixel
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1347—Arrangement of liquid crystal layers or cells in which the final condition of one light beam is achieved by the addition of the effects of two or more layers or cells
- G02F1/13475—Arrangement of liquid crystal layers or cells in which the final condition of one light beam is achieved by the addition of the effects of two or more layers or cells in which at least one liquid crystal cell or layer is doped with a pleochroic dye, e.g. GH-LC cell
Abstract
The present invention relates to liquid crystal (LC) display, this display comprises a plurality of clearly boxes of shape, size and the aspect ratio of definition that have, and the most handy liquid crystal components that contains dichroic dye of these boxes is filled.The invention still further relates to the novel method of making above-mentioned LCD.According to a kind of LCD of the present invention, comprise a plurality of display boxes, by sealant sealing, with liquid crystal components fill, and described sealant in position harden respectively by wherein said display box for described display box.According to a kind of method of making LCD of the present invention, described method comprises the display box of filling display box and filling with the sealant sealing process of sclerosis in position with liquid crystal components.
Description
The application is that the name of submitting to October 31 calendar year 2001 is called the dividing an application of No. 01134412.1 patented claim of " a kind of transmission-type of improvement or reflective liquid-crystal display and novel method for making thereof ".
A) the technical field of the invention
The present invention relates to comprise the LCD of the box with clear and definite shape, size and aspect ratio, this box is filled with liquid crystal, preferably adopts the object dyestuff to fill; The invention still further relates to the novel process for preparing of LCD.
B) background technology
Polymer Dispersed Liquid Crystal (polymer dispersion film) (PDLC) shows and generally includes two transparent plates that have electrode, is disposed opposite to each other and separates with spacer.Polymer dispersed liquid-crystal film is encapsulated between two plates.Polymer dispersed liquid-crystal film can reach 200 micron thickness, but its thickness is between 2 microns to 50 microns usually.Box seals, and purpose is to eliminate oxygen and moisture, and oxygen and moisture can cause chemical erosion to liquid crystal.P.S.Drzaic's " dispersed liquid crystal type " (1995) one books are seen in the detailed commentary of Polymer Dispersed Liquid Crystal technology.
Polymer Dispersed Liquid Crystal is made up of the micron-scale droplet that is scattered in the low-molecular-weight nematic liquid crystal in the polymer adhesive usually.To the strong scattered light of row droplet, this material has White-opalescent or translucent outward appearance (" off state ").When applying voltage difference between two electrodes (" on-state "), electric field makes particle alignment, thus the normal refraction rate of liquid crystal almost the refractive index with isotropic polymer matrix is consistent, reduced the scattering power of particulate significantly, light can be passed through.In on-state, box thereby seem bright or transparent; At off state, box is then opaque.
In object-main body (guest-host) polymer dispersed liquid crystal display, dyestuff particularly pleochroism or dichroic dyestuff is added in the liquid crystal as object, thereby makes the display of high color contrast.For example, because this dye molecule has the performance that is arranged in parallel with liquid crystal molecule, if a kind of dichroic dye with clavate structure is added in the liquid crystal, if by apply the direction that electric field changes liquid crystal molecule on electrode of opposite, the direction of dye molecule also can change.Because this dyestuff is to be used for painted or irrelevant with orientation, thereby might colored state (" off state ") and colourless state (" on-state ") be changed by apply voltage on two electrodes.Known in the art, in object-main polymer dispersed liquid crystal display, use dichroism or pleochromatic dyestuff can improve contrast.
Polymer dispersed liquid crystal display can be transmission-type and/or reflective.The transmission-type polymer dispersed liquid crystal display has an interior lighting light source.Make light can pass through box two electrode application voltage.An exemplary of transmission-type polymer dispersed liquid crystal display is a Polymer Dispersed Liquid Crystal top projector.Reflective polymer dispersed liquid crystal display generally includes the black of reflection or painted color filter, and as seen it can become in pellucidity.In personal digital assistant device (PDA) device, can find reflective polymer dispersed liquid crystal display.Owing to need not to use polariscope, transmission-type and reflective polymer dispersed liquid crystal display are attractive especially.Polariscope reduces light significantly and reduces direct-viewing type and the brightness of projection displays.There is not polariscope also can provide better visual angle.
Polymer dispersed liquid crystal display with technology preparation formerly has many shortcomings.For example: the droplet in the Polymer Dispersed Liquid Crystal has very wide Size Distribution usually, and this causes obvious hysteresis, higher operation voltage, poor contrast, disagreeable red gum spot and low-level multipath transmission.Yet the hysteresis of polymer dispersed liquid-crystal film must be lower so that show repeatably gray scale, and for the application of most of personal digital assistant devices, the low voltage operating of instrument and high-contrast are basic demands.United States Patent (USP) the 5th, 835, No. 174 (Clikeman etc.), the 5th, 976, No. 405 (Clikeman etc.) and the 6th, 037, No. 058 (Clikeman etc.), point out us to use monodispersed liquid crystal particle in the micro-meter scale scope, lag behind and operating voltage to reduce, and improve multiplex level.Concerning great majority are used, still lower with the contrast of the Polymer Dispersed Liquid Crystal device of monodisperse particles preparation.The not thickness of sacrificial polymer dispersed liquid-crystal film and operating voltage in order to improve contrast need the object dyestuff, preferred pleochroism dyestuff or dichroic dye.Yet the method for prior art can not accurately be encapsulated into the object dyestuff of high concentration in liquid crystal phase in preparation process, thereby, dyestuff that only can the inclusion low concentration in monodisperse polymer particles.Some object dyestuff may be stayed the outside of particle, thereby causes the increase of Dmin (background minimum light density) and contrast to reduce.
People wish to produce single dispersion liquid domain very much, and this can reduce requirement, acquisition high-contrast and the high-caliber multipath transmission to high operation voltage and reduce lag-effect.
The invention summary
First aspect of the present invention is about liquid crystal (LC) display, and it comprises all essentially identical box of shape, size and aspect ratio.This box preferably adopts the liquid crystal that contains the object dyestuff to fill.
Another aspect of the present invention relates to the novel method for preparing this LCD.
The invention still further relates to the preparation of shape, size and the essentially identical box of aspect ratio.Encapsulation preferably contains the liquid crystal of object dyestuff in the box, and is made by the miniature cup of making according to the present invention.In brief, the method for preparing miniature cup relates to: coat thermoplasticity or thermoset precursors thing layer on the conducting film with the mold pressing of preformed punch, then before thermoplasticity or the sclerosis of thermoset precursors thing layer, during or carry out the demoulding afterwards, sclerosis is by radiation, cooling, solvent evaporation or additive method.On the other hand, miniature cup can be made with following method: graph exposure is coated with the conducting film of radiation-curable layers, removes unexposed area in sclerosis back, exposure area then.According to LCD of the present invention, wherein said object dyestuff is a kind ofly to lose lustre or add color system.
Can prepare with any method of above-mentioned two kinds of methods and to have the miniature cup of the anti-molten and thermo-mechanical robust of monodispersed size and dimension basically.For most of display application, the range of size of miniature cup is from sub-micron to 10 micron, preferred 0.5 micron to 5 microns.Miniature cup can be an arbitrary shape, has the more shape of the large interface total area between liquid crystal and the miniature cup although preferably make.Fill miniature cup and sealing with the liquid crystal that preferably contains the object dyestuff then.
The miniature cup that another aspect of the present invention relates to being filled with liquid crystal seals, and is preferably the liquid crystal that contains the object dyestuff.Can seal with several different methods, preferable methods is before filling step, the sealant compositions that contains thermoplasticity or thermoset precursors thing to be disperseed in liquid crystal phase.Sealant compositions is not dissolved each other with liquid crystal and is had the proportion lower than liquid crystal.After the filling, thermoplasticity or thermoset precursors thing are separated, and form the floating layer in surface on liquid crystal.So can finish the sealing of miniature cup easily by sclerosis precursor layer, the sclerosis of precursor layer can utilize solvent evaporation, interfacial reaction, moisture, heat or radiation to finish.Though the combination of above-mentioned two or more curing mechanisms can be used to increase the sealing turnout, ultraviolet light (UV) radiation is the method for optimizing of sealing miniature cup.Alternatively, also can seal miniature cup with the sealant compositions coating of liquid crystalline that contains thermoplasticity or thermoset precursors thing.The solvent that uses in sealant compositions is very crucial.Solvent preferably and liquid crystal does not dissolve each other and proportion is low than liquid crystal.In order to guarantee good coating homogeneity, the viscosity of control surface tension force and sealant compositions is also very important.Finish sealing by the sclerosis sealant compositions then, sclerosis then is to finish by the combination of solvent evaporation, interfacial reaction, moisture, heat, radiation or curing mechanism.These encapsulating methods also are features of the present invention.
Another aspect of the present invention is that liquid crystal display does not have hysteresis phenomenon.Liquid crystal display device of the present invention is made up of monodispersed miniature cup basically, is filled with liquid crystal in this miniature cup and preferably is filled with the object dyestuff.Component to miniature cup is optimized, and the general refractive index of the isotropic refractive index of miniature cup and liquid crystal is complementary like this.In a kind of mode similar to the traditional polymer dispersed liquid crystal display, LCD of the present invention is strong scattered beam when not having electric field (" off state ").When applying voltage difference between two electrodes, electric field is arranged liquid crystal and is reduced its scattering power to a great extent, thereby allows light by " on-state " transmission.Yet different with Polymer Dispersed Liquid Crystal is, liquid crystal display of the present invention is issued to limpid state on the greatest optical at much lower voltage, can be returned to initial " opening circuit " state and do not have undesirable hysteresis when stopping to apply voltage.For the low power consumption that presses for, can repeat gray scale and video frequency, it is crucial that low operating voltage of the present invention, fast response time and the display that does not have a hysteresis are used high quality displayer.
Another aspect of the present invention relates to the preparation of the LCD that is made of the stack of multilayer miniature cup.This method step comprises: prepare the ground floor miniature cup with above-mentioned any method on conductive substrate, fill miniature cup with liquid crystal components, sealing comes the miniature cup of stacked sealing at last with second conductive substrate that scribbles adhesive phase in advance.Bonding agent can be a hotmelt, the bonding agent that is heating and curing, moisture-curable bonding agent or radiation-curing binders.Making us interested especially is to have used ultraviolet light curing adhesive in the present invention.For improving contrast, can use the above miniature cup array of one deck.This method step comprises: the preparation miniature cup, fill with liquid crystal components, and sealing, with the miniature cup array of second layer miniature cup formation component coating or stacked sealing, second miniature cup array is shaped with any method of describing in the past (preferably die pressing); The following step of repeated several times, i.e. the filling of miniature cup and sealing forms the miniature cup of component coating or stacked sealing with another layer miniature cup, last on which floor miniature cup stacked precoating second conductive substrate of adhesive phase is arranged.The preformed punch used of preparation miniature cup be before thermoplasticity or the sclerosis of thermoset precursors thing layer, during or carry out the demoulding afterwards
Another aspect of the present invention relates to the method that conductive substrate that utilization scribbles (red, green, indigo plant) color filter and preferred black substrate in advance prepares the full color reflective LCD.Alternatively, full-color display can prepare with following step: be layered on the preformed miniature cup with one deck positive photoresist, optionally open the miniature cup of some by the graph exposure positive photoresist, described etchant resist then develops, fill the miniature cup of opening with the liquid crystal components that contains object dyestuff (dichroic dye of preferred first look), seal the miniature cup of having filled with aforementioned encapsulating method.These steps can repeat, to make the miniature cup of the sealing of filling the liquid crystal components that contains the second or the 3rd look object dyestuff.Available black substrate improves contrast and color saturation.
The rapid method of the multistep of these disclosures can roll-to-roll continuous or semi-continuous carrying out.Thereby they are suitable in enormous quantities and low-cost production.With other large-scale production process comparatively speaking, these production methods also are efficient and cheaply.LCD according to the present invention's preparation is insensitive to environment, particularly to humidity and temperature-insensitive.This display can be very thin, flexible, durable, easy operating and a great variety of modelsization.Because the LCD according to the present invention's preparation comprises a plurality of boxes with gratifying aspect ratio and monodispersed substantially shape and size, so the display of making according to the present invention shows many perfect performance, as low power consumption, fast response time, high-caliber multipath transmission, high-contrast and owing to there not being undesirable hysteresis to have repeatably gray scale.
According to LCD of the present invention, box is wherein made by aperture area about 1 to the miniature cup of about 25 square microns; The degree of depth of box about 0.5 is to about 10 microns; The opening of box and the ratio of wall are about 0.2 to about 9; The glass temperature range of used thermoplasticity or thermoset precursors thing layer is from-20 ℃ to about 100 ℃ approximately in the manufacture process.Thermosetting among the present invention or thermoplastic precursors thing material are selected from: acrylate, methacrylate, vinyl compound, the acrylate of multivalence, the methacrylate of multivalence, cyanoacrylate, the vinyl compound of multivalence, the epoxide of multivalence, the isocyanates of multivalence, the propenyl compound of multivalence, and oligomer of deriving or polymkeric substance
Accompanying drawing is briefly described
Fig. 1 a, 1b show typical Polymer Dispersed Liquid Crystal device " shutoff " and " connection " state respectively.
Fig. 1 c, 1d and 1e are the synoptic diagram of LCD of the present invention.
Fig. 2 a-2d illustrates a kind of typical method for preparing little mold pressing punch.
Fig. 3 a-3b represents to make the roll-to-roll method of LCD, thereby particularly scribbles the conducting film formation miniature cup of ultraviolet light polymerization component by mold pressing.
Fig. 4 a-4b shows two scanning electron microscope (SEM) microphoto of the miniature cup array made from little mold pressing.
Fig. 5 a1,5a2,5b1,5b2,5c1 and 5c2 are the optional method steps of preparation miniature cup, relate to ultraviolet radiation the conducting film that scribbles the thermoset precursors thing is carried out graph exposure.
The example of the miniature cup array of Fig. 6 a to 6f signal difformity and pattern.
Fig. 7 is the process flow diagram of preparation monochromatic liquid crystal display.
Fig. 8 a to 8h signal prepares the method for full-color display with three primary colors object dyestuff.
Fig. 9 a is the typical hysteresis curve of traditional Polymer Dispersed Liquid Crystal device.
Fig. 9 b shows in the typical miniature cup LCD of the present invention does not have hysteresis loop.
Detailed Description Of The Invention
Definition
Unless definition is arranged in addition, otherwise all the common habitual definition of using and understanding is used according to those skilled in the art at this used technical term in patent specification.
" miniature cup (microcup) " word refers to the recess of the cup-shaped that generated by little mold pressing or graph exposure.
In patent specification, term " box " refers to by the formed independently unit of a sealing miniature cup. These boxes are filled with the liquid crystal that preferably contains the object dyestuff.
When explanation this miniature cup or box, term " has clearly defined " to refer to that this miniature cup or box have clear and definite shape, size and the aspect ratio predetermined according to the special parameter of this manufacture method.
When this miniature cup of explanation or box, term " monodispersed " refers to that described miniature cup or box have narrow distribution of sizes, such as diameter, length, width and height.
" aspect ratio " word is the vocabulary known to general in the polymer dispersed liquid crystal display. In this application, its degree of depth of referring to miniature cup is to width or the degree of depth ratio to length.
Preferred embodiment
As shown in Figure 1a, typical polymer dispersed liquid crystal display comprises two battery lead plates (10,11), and one of them is that transparent electrode (10) and one deck are scattered in the liquid crystal territory in the isotropic polymer matrix.Fig. 1 a also shows, when when not applying voltage (13) on two battery lead plates (10,11), and the liquid crystal molecule random alignment.Because of making incident light (14), the random arrangement of liquid crystal molecule forms scattered light (15).
Fig. 1 b shows that when applying voltage (13) on two battery lead plates, liquid crystal molecule is pressed certain orientation and arranged.Incident light (16) thereby can form transmitted light (17) is because the common refractive index of liquid crystal and isotropic refractive index of polymer substrate (12) are complementary.
Shown in Fig. 1 c, monochromatic liquid crystal display of the present invention comprises the clearly box (18) of definition that has that is encapsulated between two electrodes (10,11).These boxes have essentially identical shape and size, and fill with liquid crystal components.Electrode in observer's one side is transparent, and this two electrode has at least one to be patterning.As using (Fig. 1 d) trisimulus filter (19), then can obtain FR color as red (R), green (G) and blue (B).
Alternatively, be filled with the clearly box (1,2 and 3) of definition, then can obtain according to full-color display of the present invention to contain liquid crystal components red, green and bluehacker body dyestuff (preferred dichroic dye) respectively.For example, fill box (1), fill adjacent box (2), fill adjacent box (3) with the liquid crystal that contains blue object dyestuff with the liquid crystal that contains green object dyestuff with the liquid crystal that contains red object dyestuff.The number of plies that the box of liquid crystal is housed can be more than one deck (Fig. 1 e).
The method that is used to prepare this LCD relates to several aspects.
I.
The preparation of miniature cup
(a) preparation of punch
Can use photoetching process earlier, then adopt etching or electric plating method to prepare punch.Make the representative embodiment of punch and see Fig. 2 a to 2d.(Fig. 2 a) goes up the spraying plating skim at a glass substrate (20) and is generally 3000 when adopting electrochemical plating
Seed metal (21), inconel (chrome inconel) for example.Then be coated with one deck photoresist (22), and with ultraviolet photoetching.One mask (24) is placed between ultraviolet light and the photoresist layer (22).The exposure area hardening of this photoresist.Clean with appropriate solvent then, remove unexposed area.The dry sclerosis photoresist that keeps, and the seed of spraying plating skim once more metal.(Fig. 2 b) is ready for main then mould, can carry out electrotyping process.The typical material that is used for electrotyping process is nickel cobalt (alloy) (23).In addition, this main mould can be made by nickel, as photo-optics Instrumentation Engineering teacher association journal volume 1663, " the continuous making of flash plating optical medium " (" Continuous manufacturing of thin cover sheetoptical media " among the pp.324 (1992), SPIE Proc.) illustrates in, adopt nickel sulfamic acid (nickelsulfamate) to electroplate or electroless nickel deposition.The base plate of this mould (Fig. 2 d) is generally 1 to 5 micron.This main mould also can be made of other little engineerings, comprise that electron beam writes, dry type is lost agent, chemical corrosion agent, laser writes or laser interference, as photo-optics Instrumentation Engineering teacher association journal " precision optics reproduction technology " (" Replicatio techniques formicro-optics ", SPIE Proc.) volume 3099, explanation among the pp.76-82 (1997).In addition, this mould can use plastics, pottery or metal, utilizes the light processing and fabricating.
(b) miniature cup is made in mold pressing
This method step is shown in Fig. 3 a and 3b.Punch (30) can place on the supporting network (web) (34) that (Fig. 3 is a) or under the supporting network (Fig. 3 b).On glass plate or plasticity substrate, form a nesa coating (31), make transparent conduction base sheet.On this conducting film, be coated with one deck thermoplasticity or thermoset precursors thing (32) then.Under the glass temperature condition that is higher than thermoplasticity or thermoset precursors thing layer, this thermoplasticity or thermoset precursors thing layer are carried out mold pressing with roller, plate or band punch.
Be used to prepare the thermoplasticity or the thermoset precursors thing (32) of miniature cup (33), can be the acrylate of multivalence or methacrylate, the vinyl compound (for example vinyl benzene, vinyl silanes and vinethene) of multivalence, the propenyl compound of multivalence, and the oligomer, polymkeric substance, epoxide that comprise crosslinkable functionality with and oligomer, polymkeric substance and analog, this oligomer or polymkeric substance are to contain the oligomer of crosslinkable functionality or the derivant of polymkeric substance.The preferably acrylate of multivalence and oligomer thereof.The combination of the epoxide of multivalence and the acrylate of multivalence also is very beneficial for obtaining needed physical and mechanical properties.Usually, also add and give flexible crosslinkable oligomers, for example urethanes acrylate or polyester acrylate are to improve the bending resistance of mold pressing miniature cup.This component can comprise polymkeric substance, oligomer, monomer and adjuvant, perhaps has only oligomer, monomer and adjuvant.The glass temperature of this class material (Tg) scope is generally-70 ℃ to about 150 ℃ approximately, is preferably-20 ℃ to 50 ℃ approximately.Little mould pressing method normally carries out being higher than under the glass temperature.Can adopt the heating punch, or the heated mould submounts, to control the temperature and pressure of little mold pressing.
Shown in Fig. 3 a and 3b,, appear miniature cup (33) array between hardening period or the sclerosis back demoulding of precursor layer.Can make the sclerosis of precursor layer with cooling, radiation crosslinking, heat or moisture.If come the cured thermoset precursor with ultraviolet radiation, ultraviolet light then can be radiated on the nesa coating from the bottom or the top of supporting network (34), shown in above-mentioned two figure.In addition, ultraviolet lamp can place mould inside.In this case, mould must be transparent, thereby allows ultraviolet light to be radiated on the thermoset precursors thing layer by the punch of pre-patterning.
Fig. 4 a and 4b are the scanning electron microscope microphotos by two miniature cup arrays of little mold pressing preparation.
(c) prepare miniature cup with graph exposure method
In addition, by a mask (50), (Fig. 5 a) also can prepare miniature cup coating radiation curing material (51) graph exposure on the conducting film (52) with ultraviolet light or other forms of radiation.Conducting film (52) is on plastic substrate (53).
Concerning roll-to-roll method, photomask can be synchronous with supporting network, moves with the speed identical with the latter.In the photomask (50) of Fig. 5 a, darkened boxes (54) expression zone of opacity, the interval between the darkened boxes (55) are the open areas.Ultraviolet light is radiated on the radiation curing material by open area (55).The exposure area hardening is removed unexposed area (zone of opacity by this mask is protected) with appropriate solvent or developer then, thereby forms miniature cup (56).This solvent or developer are selected from those solvents that is commonly used to dissolve or disperse radiation adjustable curing material, as butanone, toluene, acetone, isopropyl alcohol or its analog.
Fig. 5 b and 5c illustrate two kinds of other optional methods making miniature cup of graph exposure.These two figure characteristics are basic the same with characteristics shown in Fig. 5 a, and appropriate section has adopted same numbering.In Fig. 5 b, the conducting film of use (52) is opaque and pre-patterning.In this case, help carrying out graph exposure by conductive film figure radiation-sensitive material, wherein this conductive film figure is as photomask.Behind ultraviolet radiation, remove unexposed area and then can make miniature cup (56).In Fig. 5 c, conducting film (52) also is opaque and distinguishes band-patterning.See through conducting film district band-pattern (52), from the bottom radiation curing material is exposed, wherein conducting film district band-pattern is as first photomask.Carry out re-expose by second photomask (50) from another side, second photomask has the district band pattern vertical with conducting film district band.Thereby remove unexposed area with solvent or developer then and manifest miniature cup (56).
In general, miniature cup (56) can be to make the maximized Any shape of liquid crystal territory light scattering effect.Miniature cup in a system has essentially identical size and dimension.Yet the miniature cup of difformity and size can be used for different colours.For example, the miniature cup of filling with the liquid crystal that contains red object dyestuff can have different shapes or size with green miniature cup or blue miniature cup.And a pixel can comprise the miniature cup of the different numbers with different colours.In addition, a pixel can comprise some less green miniature cups, the red miniature cup that some are bigger and the blue miniature cup that some are less.Concerning these three kinds of colors, there is no need to be of similar shape and number.Fig. 6 a to 6f has illustrated the example that can be used for 6 kinds of miniature cup patterns of the present invention.
The opening of miniature cup can be circle, square, rectangle, hexagon or any other shape.It is less that separation area between the opening preferably will keep, so that obtain high colour saturation and high-contrast in the desirable mechanical property of maintenance.
For LCD of the present invention, the range of size of single miniature cup can be from about 0.04 to about 100 square microns, preferably from about 0.6 to about 36 square microns.The depth range of miniature cup is about 1 to about 10 microns, preferably from about 2 to about 6 microns.Opening is approximately 0.05 to about 20 to the proportional range of wall, is preferably about 0.2 to 10 micron.Normally about 0.5 to 6 micron to the distance range at edge of edge of opening is preferably about 1 to about 4 microns.
II.
Liquid crystal, dichroic dye and composition thereof
Usually adopt coating process, fill the miniature cup array that forms like this with liquid crystal.Dichroic dye can also be contained in the liquid crystal so that give this display monochrome and increase contrast.
Prior art is known to can be used for liquid crystal material of the present invention.Can be used for liquid crystal material embodiment indefiniteness of the present invention ground and comprise E7, TL205, TL213, BL006, BL009 and BL037 from German E.Merck company.Other liquid crystal materials are listed in United States Patent (USP) the 5th, 835, in 174 (Clikeman etc.).Also can use cholesteric liquid crystal in some applications.
Liquid crystal among the present invention preferably contains the object dyestuff.Object dyestuff of the present invention is a dichroic dye, and is known by the present technique field.United States Patent (USP) the 5th, 589, No. 100 (Grasso etc.) point out that azo aryl (arylazo) or poly-azo aryl dichroic dye can use with liquid crystal, and have enumerated and be applicable to other dichroic dye of the present invention.
The adding dyestuff is not only and has been added color, and on the certain degree some display application has been improved contrast.In order to be suitable for, dyestuff must have high preface parameter and the suitable solubility in the main body liquid crystal material.Have bigger molecular length width ratio and the microscler dyestuff that is similar to liquid crystal material of main part molecular shape have been promoted high order parameter.The liquid crystal that contains the object dyestuff can provide good visual characteristic, as high-contrast, high extinction, and chemistry and photochemical stability.The embodiment of the dichroic dye with high dichroism ratio of Shi Yonging comprises blue AB2, red AR1 and the yellow AG1 of German Funktionfluid Gmb company in the present invention, and the SI-486 (yellow) of Mitsui Toatsu company, SI426 (redness), M483 (blueness), S344 (black), S428 (black) and S7 (black).
Nonionic azo and anthraquinone dye are also used very much.Comprise to the embodiment indefiniteness: the oil red EGN of Arizona State Pylam Products company (Oil Red EGN), tonyred (Sudan Red), the Sudan's indigo plant (Sudan Blue), solvent blue (Oil Blue), Macrolex indigo plant, solvent blue 35 (Solvent Blue 35), Pylam Spirit deceive and Fast Spirit deceives, the Sudan black B of Aldrich company (Sudan Black B), the Thermoplastic of BASF AG deceives X-70, and the anthraquinone blue of Aldrich company, anthraquinone Huang 114, anthraquinone is red 111,135, anthraquinone green 28.In any case, in the miniature cup material dyestuff must be chemically stable, and should have low solubility.Liquid crystal or dyestuff should corrode miniature cup at no time.
III.
The sealing of miniature cup
The available several different methods of the sealing of miniature cup is finished.A kind of preferable methods is that the ultraviolet light polymerization sealant compositions is scattered in the liquid crystal components.This ultraviolet light polymerization component and liquid crystal do not dissolve each other, and have the proportion lower than liquid crystal.The ultraviolet light polymerization component is radially being mixed in the mixer fully with liquid crystal components, and adopts as accurate coating machinery devices such as Myrad rod, gravure plate, wing, fluting coating or the coatings of cracking, coats immediately on this miniature cup.Volatile solvent can be used for controlling the cladding thickness of viscosity, coating, and is convenient to sealant and separates from liquid crystal phase.Available sweep the bar scraper or similarly device excessive fluid is struck off.Then dry the miniature cup of filling, this ultraviolet light polymerization component floats over the top of liquid crystal.During the ultraviolet light polymerization layer rises to the surface or afterwards, it is cured (original position sclerosis), the sealing miniature cup.Ultraviolet light or other forms of radiation as visible light, infrared ray, and electron beam etc., all can be used for this miniature cup is solidified and sealing.Alternatively, when using heat or moisture-curable sealant compositions, also can use heat or moisture or its array mode that this miniature cup is solidified and sealing.
The usable surface activating agent improve the cohesive of sealant and miniature wall of cup and improve liquid crystal and encapsulant between the wetting state at interface.Useful surfactant comprises the FC surfactant of 3M company, Zonyl fluorinated surfactant, fluorinated acrylic ester, fluorinated methyl acrylate, fluoro long-chain alcohols, the long-chain carboxylic acid of perfluor replacement and the Silwet surfactant of derivant and Osi company thereof of DuPont company.
Alternatively, liquid crystal and sealant compositions can be coated miniature cup successively.Like this, can be by coating one deck thermoplasticity or thermoset precursors thing component thin layer (this precursor component is that radiation, heat, moisture or interfacial reaction are curable), and it is solidified on the miniature cup surface through filling, to finish this seal process.Carry out ultraviolet light polymerization after the interfacial polymerization, very favourable for seal process.Form a thin separate layer by interfacial polymerization, the mutual mixing between liquid crystal layer and the outer coating layer obviously is inhibited.Then finish sealing, be preferably ultraviolet radiation by the back curing schedule.For further reducing the degree of mixing mutually, preferably the proportion of outer coating layer is lower than the proportion of liquid crystal.Available volatile organic solvent is adjusted the viscosity and the thickness of coating.Outside volatile solvent is used for during coating layer, be preferably with this liquid crystal or this dyestuff not misciblely, and its proportion is lower than the proportion of liquid crystal phase.This two go on foot coating processes, used dyestuff are dissolved at least in part the situation particularly suitable of sealant layer.For further reducing the degree of mixing mutually of sealant layer and liquid crystal phase, before the coating sealant layer, can carry out the chilling cooling to miniature cup array through filling.
Alternatively, peel off the substrate transfer layer from one and fold an adhesive phase to miniature cup, preferably then come the curing adhesive layer, remove at last and peel off substrate, thereby finish the sealing of miniature cup with heat, radiation or simple solvent evaporation through filling.The chilling cooling miniature cup through filling also helps the seal process that carries out with the transfer laminating method.
IV.
The preparation of monochromatic liquid crystal display
By flowchart text the method shown in Figure 7.All miniature cups all use the liquid crystal that contains same color object dyestuff to fill.This method can be continuous roll-to-roll method, comprises the steps:
1. go up coating one deck thermoplasticity or thermoset precursors thing (70) at a nesa coating (71), optionally have solvent.If any solvent, solvent should evaporate easily.
2. be higher than under the condition of thermoset precursors thing layer glass temperature in temperature, with preformed punch (72) molded thermoplastics or thermoset precursors thing layer.
3. from thermoplasticity or thermoset precursors thing pull-up mould, preferably carry out between hardening period or afterwards in a suitable manner in thermoplasticity or thermoset precursors thing layer.
4. fill the miniature cup array (73) that said method is made with the liquid crystal components (74) that contains thermoset precursors thing component, this thermoset precursors thing component is incompatible and lower than the proportion of liquid crystal phase with liquid crystal.
5. separate and this forms floating layer an of surface above liquid crystal phase during or afterwards at this thermoset precursors thing, by this thermoset precursors thing sclerosis is sealed miniature cup, preferred employing solvent evaporation, radiation be ultraviolet light (75) or heat or moisture for example, and forms the encapsulated liquid crystals box that includes liquid crystal and preferred object dyestuff.
6. second conducting film (76) that precoating is furnished with adhesive phase (77) is layered on the liquid crystal cell array of sealing, and wherein said adhesive phase (77) can be contact adhesive, hotmelt, heat, moisture or radiation-curing binders.
Can be with heating or radiation such as ultraviolet light (78), by this top conductive film to adhesive phase harden (if this top conductive film is transparent to this class radiation).Product after stacked can be cut (79) to suitable size, is used for the assembling of device.
The operation that the preparation of above-mentioned miniature cup can be made with another kind of graph exposure easily replaces, and promptly the conducting film that is coated with the thermoset precursors thing is carried out graph exposure, then removes unexposed area with a kind of appropriate solvent.Can follow the miniature cup lip-deep sealant of sclerosis by aforesaid coating or transfer coated method, thereby finish sealing miniature cup through filling.
For improving contrast, can use the above miniature cup array (Fig. 1 c) of one deck.Thereby (step 5) forms component to another layer miniature cup and is coated on the miniature cup array of sealing after the sclerosis of the sealant on the miniature cup through filling.Step 2 can repeat several times the contrast that is fit to up to obtaining to 5.Be laminated in this multilayer miniature cup with second conductive layer then, and be cut into suitable size to be used for the display assembling.Be important to note that having one deck in the two-layer conducting film at least is pre-patterning.And be transparent at the conducting film of observer's one side at least.
V.
The preparation of polychrome device of liquid crystals
Polychrome device of liquid crystals of the present invention can utilize (red, green, indigo plant) color filter and a kind of black matix to be made, and this black plastid is placed at following (Fig. 1 d) of the monochrome display of prosthomere making.Alternatively, full-color display of the present invention can be made (Fig. 1 e) by filling miniature cup with the liquid crystal that contains different colours object dyestuff.Except described method when making monochrome display, need extra step to prepare such color monitor.These extra steps comprise: (1) is layered in a kind of positivity action dry film photoresist on the miniature cup of making, this photoresist is grouped into by following one-tenth: at least a support membrane (PET-4851 that is produced as the Saint-Gobain company of Massachusetts Worcester) of removing, phenolics positive photoresist (as the MicropositS1818 of Shipley company), and a kind of alkaline development adhesive phase (as the potpourri of the Carboset 515 of the Nacor72-8685 of National Starch company and BF Goodrich company); (2) by photoresist is carried out graph exposure, remove and to remove support membrane, and use a kind of developer, as diluted Microposit 351 developers of Shipley company, this positive photoresist is developed, thereby optionally open the miniature cup of some; (3) fill the miniature cup of opening with the liquid crystal that comprises the first primary colors object dyestuff; And (4) seal the miniature cup through filling according to the method for explanation in the monochrome display preparation.These extra steps can repeat, to form with second and the miniature cup of trichromatic liquid crystal filling.
More particularly, can prepare a kind of polychrome device of liquid crystals according to step shown in Figure 8.
1. go up coating one deck thermoset precursors thing (80) at conducting film (81).
2. be higher than under the condition of its glass temperature in temperature, with preform punch (not shown) this thermoplasticity of mold pressing or thermoset precursors thing layer.
3. preferably by solvent evaporation, cooling, radiation, heat or moisture-crosslinking between hardening period or afterwards, at thermoplasticity or thermoset precursors thing layer with this punch from this thermoplasticity or thermoset precursors thing pull-up mould.
4. go up a stacked positive dry film photoresist at the miniature cup array of making like this (82), wherein comprise a kind of positive photoresist (84) at least, and a kind of removable plastics screening glass (not shown).This positive dry film photoresist can comprise an adhesive phase (83), to improve the cohesive between miniature cup and this photoresist.
5. with ultraviolet light, visible light or other radiation this positive photoresist is carried out graph exposure (Fig. 8 c), remove screening glass, develop in the exposure area and open miniature cup.Step 4 and 5 purpose are optionally to open some miniature cups (Fig. 8 d) in a presumptive area.
6. fill the miniature cup open with liquid crystal components, this liquid crystal components comprise first primary colors object dyestuff (85) and with the inconsistent sealant compositions of this liquid crystal phase (86), and this liquid crystal phase proportion of sealing agent ratio of component is low.
Sealant separate and on liquid crystal phase, form the floating layer in a surface during or afterwards, adopt solvent evaporation, or preferred ultraviolet radiation, be preferably heat or moisture-curable method sclerosis sealant layer, seal miniature cup, comprise the sealing liquid crystal cell (Fig. 8 e) of the liquid crystal of the first primary colors object dyestuff with formation.
8. can repeat above-mentioned steps 5 to 7, so that produce the clearly box (Fig. 8 e, 8f and 8g) of definition that has of the liquid crystal comprise different colours object dyestuff in zones of different.
9. precoating is furnished with one second nesa coating (87) of adhesive phase (88), is layered on the liquid crystal cell array of sealing, wherein said adhesive phase can be contact adhesive, hotmelt or a kind of heat, moisture or radiation-curing binders.
10. curing adhesive.
The preparation of the miniature cup in the said method, can replace with another kind of operation easily: graph exposure is coated with the conducting film of thermoset precursors thing, then removes unexposed area with a kind of appropriate solvent.In addition, can finish sealing by directly being coated with and cured thermoset precursor component layers on the liquid crystal phase surface to miniature cup.
Display with this method manufacturing can reach the only thickness of a piece of paper.The width of this display is the width (being generally 3 to 90 inches) of coating supporting network.The length of this display can be any length, can depend on the size of volume from several inches to several thousand feet.
Embodiment
Below described embodiment, be can more clearly understand and put into practice the present invention for ease of those skilled in the art.These embodiment should not be construed as and limit the scope of the present invention, and only are to explanation of the present invention and demonstration.
Prepare miniature cup with little mould pressing method
Component shown in the table 1 is applied to the Sheldahl company that scribbles in advance with Myrad rod #6, and (Northfield is on 2 Mills (mil) the PET film of ITO conductive film layer MN).One preform (4 * 4 * 4 microns) nickel cobalt (alloy) punch and be used for little mold pressing from the demoulding Frekote700-NC of Henkel company.Coating thickness is controlled at about 5 microns.Then under 90 ℃, by means of a pressure roll, with masterplate mold pressing coated film.Employing has the curing area band exposure device (from ADAC Technologies company) of metal fluorine lamp, is 80 milliwatt/square centimeters in 365 nanometer light intensities, by polyester resin film, coating is carried out ultraviolet light polymerization about 1 minute.The demoulding from the film tool of film after the mold pressing manifests the clearly miniature cup of definition (4 * 4 * 4 microns).Little die forming is finished with the GBC laminating machine down at 90 ℃.
Table 1: the ultraviolet curing acrylic Recipe that is used to make miniature cup
| Numbering | Explanation | Composition | The | Umber | |
| 1 | Epoxy acrylate | Ebecryl?600 | UCBChemicals | 55 | |
| 2 | Polyester acrylate | Ebecryl?830 | UCBChemicals | 15 | |
| 3 | The urethanes acrylate | Ebecryl?6700 | |
10 | |
| 4 | Si acrylate | Ebecryl?350 | UCBChemicals | 5 | |
| 5 | | SartomerSR238 | Sartomer | 10 | |
| 6 | Monomer | SartomerSR306 | Sartomer | 5 | |
| 7 | Monomer | SartomerSR351 | Sartomer | 5 | |
| 8 | Light trigger | Irgacure?500 | |
1 | |
| 9 | Reinforcing agent | Methyldiethanolamine | Aldrich | 0.5 | |
| 10 | Solvent | Butanone | Aldrich | 100 |
Prepare miniature cup with little mould pressing method
Identical with embodiment 1, difference is that employing table 2 prescription is coated with, and carries out mold pressing with 4 * 4 * 4 microns punch.
Table 2: the ultraviolet curing acrylic Recipe that is used to make miniature cup
| Numbering | Explanation | Composition | The | Umber | |
| 1 | Epoxy acrylate | Ebecryl?600 | UCB? |
50 | |
| 2 | Polyester acrylate | Ebecryl?830 | UCB? |
15 | |
| 3 | The urethanes acrylate | Ebecryl?6700 | UCB?Chem?icals | 10 | |
| 4 | Si acrylate | Ebecryl?350 | UCB?Chemicals | 5 | |
| 5 | Monomer | Poly-(ethylene glycol) methacrylate | Aldrich | 5 | |
| 6 | Monomer | Sartomer?SR238 | Sartomer | 5 | |
| 7 | Monomer | Sartomer?SR306 | Sartomer | 5 | |
| 8 | Monomer | Sartomer?SR351 | Sartonmer | 5 | |
| 9 | Light trigger | Irgacure?907 | Ciba | 0.5 | |
| 10 | Solvent | Butanone | Aldrich | 300 |
Use Myrad rod #12.Control thickness is 5 microns.Carry out little mold pressing with the pressure roll (GBC laminating machine) that is heated to 90 ℃.
Prepare miniature cup with little mould pressing method
Component shown in the table 3 is layered between the 2 Mill PET films and preform (4 * 4 * 4 microns) nickel cobalt (alloy) mould that scribble the ITO conductive layer in advance with pressure roll.(Chicago IL) handles 5 seconds of PET/ITO film for Electro-Technic Products company, model BD-10A with corona discharge assembly.With Frekote 750-NC release agent the nickel cobalt (alloy) mould is carried out pre-service.See through the PET/ITO film, use ultraviolet curable coating 1 minute.With the demoulding from the mould of this moulding film, manifest clearly (4 * 4 * 4 microns) of definition then, thickness is 5.5 microns miniature cup, and wherein the measurement of thickness is to adopt the Mituyoto thick gauge.
Table 3: the ultraviolet curing acrylic Recipe that is used to make miniature cup
| Numbering | Explanation | Composition | The | Umber | |
| 1 | Epoxy acrylate | Ebecryl?600 | UCB?Chemicals | 40 | |
| 2 | Polyester acrylate | Ebecryl?830 | UCB? |
15 | |
| 3 | The urethanes acrylate | Ebecryl?6700 | UCB? |
10 | |
| 4 | Si acrylate | Ebecryl?350 | UCB?Chemicals | 5 | |
| 5 | Monomer | Poly-(ethylene glycol) | Aldrich | 15 | |
| 6 | Monomer | Sartomer?SR238 | Sartomer | 5 | |
| 7 | Monomer | Sartomer?SR306 | Sartomer | 5 | |
| 8 | Monomer | Sartomer?SR351 | Sartomer | 5 | |
| 9 | Light trigger | Irgacure?907 | Ciba | 0.5 |
Embodiment 4
The preparation of the miniature cup of filling with liquid crystal solution
Earlier with hexane, the miniature cup made in embodiment 3 with the butanone flushing then, then drying 10 minutes in baking oven (66 ℃).The liquid crystal BL006 (from German E.Merck company) that contains 1% (percentage by weight) Silwet L7608 (from Osi Specialties company) mixes with the pentanone of 9 times of volumes, with Myrad rod # 16 formed solution coat on miniature cup.Unnecessary solvent in 10 minutes miniature cups of evaporation in baking oven (66 ℃).
Embodiment 5
The preparation of the miniature cup of filling with the liquid crystal solution that contains blue dichroic dye
Earlier with hexane, the miniature cup made in embodiment 3 with the butanone flushing then, then drying 10 minutes in baking oven (66 ℃).The liquid crystal BL006 (from German E.Merck company) that contains the blue AB2 of 3% (percentage by weight) dichroic dye (from German Funktionfluid Gmb company) and 1% (percentage by weight) Silwet L7608 (from Osi Specialties company) mixes with the pentanone (MPK) of 9 times of volumes, with #16 Myrad rod the solution coat of formation on miniature cup.Unnecessary solvent in 10 minutes miniature cups of evaporation in baking oven (66 ℃).
Embodiment 6
The preparation of the miniature cup of filling with the liquid crystal solution that contains black dichroic dye potpourri
The first miniature cup of using butanone (MEK) flushing in embodiment 3, to make with hexane, then, then drying 10 minutes in baking oven (66 ℃).Blue AB2, the red AR1 of three kinds of dichroic dye and yellow AG1 (from German Funktionfluid Gmb company) are mixed, make a kind of black dichroic dye potpourri.The liquid crystal BL006 that contains 2% (percentage by weight) black dichroic dye potpourri and 1% (percentage by weight) Silwet L7608 (from Osi Specialties company) (from German E.Merck company) solution is mixed with the pentanone of 9 times of volumes, with Myrad rod # 16 the solution coat that forms on miniature cup.In baking oven (66 ℃), evaporated solvent unnecessary in the miniature cup 10 minutes.
Embodiment 7
With two steps (coating) method sealing miniature cup
Vistalon 0106 with 10% (from Exxon Mobil Chemicals company) Isopar E (from Exxon Chemicals company) solution coat is on the miniature cup that the BL006 of embodiment 4,5 and 6 preparations fills.This coating is all even transparent.Use a #3Myrad rod, obtaining sealed polymer layer weight is 0.39 milligram/square inch, and thickness estimation is 0.7 micron.Use #8 Myrad rod, obtaining sealed polymer layer weight is 0.75 milligram/square inch, and thickness estimation is 1.3 microns.The density of Vistalon 0106 is about 0.9 gram/cubic centimetre.
Embodiment 8
With two steps (coating) method sealing miniature cup
According to the identical step of embodiment 7, with Amphomer28-4910 (from a kind of carbonyl acid ester (or salt) acrylic copolymer of NationalStarch company, on the miniature cup that the BL006 that 10% solution coat in the 2-propyl alcohol prepares in foundation embodiment 5 fills, thereby seal this miniature cup.This coating is all even transparent.Use a kind of #3Myrad rod, obtain the sealed polymer layer, weight is 0.44 milligram/square inch, and thickness estimation is 0.6 micron.Use #8 Myrad rod, obtaining sealed polymer layer weight is 1.0 milligrams/square inch, and the thickness estimation of sealing polymeric layer is 1.3 microns.The density of Amphomer 28-4910 is about 1.2 gram/cubic centimetres.
Embodiment 9
The polymer dispersed liquid crystal display that is separated that the conventional polymeric effect causes
For comparing purpose, prepared the polymer dispersed liquid crystal display that is separated that the conventional polymeric effect causes.Mix with Norland65 (from Norland company) with the liquid crystal E7 of different proportion (from German E.Merck company), and potpourri is clipped between the two-layer ITO coated glass plate, sept is respectively 4.5 microns, 25 microns or 50 microns.Adopt step wedge optimization to use the ultraviolet light polymerization time of curing area band exposure device (from ADAC Technologies company).Fig. 9 a is the typical hysteresis curve of the polymer dispersed liquid crystal display that is separated that causes of the polymerization by said procedure preparation.
SIPix does not have the hysteresis LCD
Miniature cup with embodiment 1,2 or 3 preparations is assembled the individual layer LCD.According to step, fill miniature cup with the liquid crystal that contains or do not contain dichroic dye in embodiment 4,5 and 6.According to the step of embodiment 7 or 8, seal the miniature cup that these liquid crystal are filled then.LCD according to the present invention's preparation be can't see hysteresis (seeing Fig. 9 b).
The assembling of multi-layer display and performance thereof
The assembling multilayer liquid crystal display is to improve the performance of display.Prepare the individual layer LCD according to embodiment 10 described methods.With identical step, at the top of ground floor LCD mold pressing second layer miniature cup, fill with the liquid crystal that contains or do not contain dyestuff, and sealing second layer LCD.When aligning second layer miniature cup on the ground floor miniature cup, second layer miniature cup departs from about 0 to 10 degree of ground floor miniature cup, so that the light scattering ability maximum.Thereby stacked two double-deck arrays are overlapped into four layers of LCD.Obtain a high-contrast display, this display has respectively～1msec and～enhancing and convergent response time of 10msec (in the time of 40 volts).Do not observe any hysteresis loop.
Claims (25)
1. a LCD comprises a plurality of display boxes, wherein:
A) described display box is a miniature cup, and described miniature cup has the partition wall that is formed by thermoplasticity or thermoset precursors thing; And
B) described display box is filled and is sealed by a sealant respectively with liquid crystal components, and described sealant hardens at the top of described liquid crystal components and in position.
2. LCD according to claim 1, wherein said sealant is formed by seal group branch, and the proportion of described sealing component is lower than the proportion of described liquid crystal components.
3. LCD according to claim 1, wherein said display box has essentially identical size and dimension.
4. LCD according to claim 1, wherein said display box right and wrong sphere.
5. LCD according to claim 1, wherein said display box are circular by opening, polygon, and hexagon, miniature cup rectangle or foursquare is made.
6. LCD according to claim 1, wherein the described display box in presumptive area is filled with the liquid crystal components of the object dyestuff that contains predetermined color.
7. LCD according to claim 6, wherein said display box is adjacent one another are.
8. LCD according to claim 6, wherein the described display box of one deck is layered in the top of the described display box of another layer.
9. LCD according to claim 1, wherein said liquid crystal components is with a kind of object dye coloring.
10. LCD according to claim 9, wherein said object dyestuff are a kind ofly to lose lustre or add color system.
11. according to claim or 1 described LCD, wherein said display comprises the miniature cup array that is filled with liquid crystal components that one deck is above.
12. LCD according to claim 1 also comprises color filter.
13. LCD according to claim 12, wherein said color filter are red, green, and blue color filter.
14. LCD according to claim 1, wherein said liquid crystal components are partially filled in each of described display box.
15. LCD according to claim 14, wherein said partially filled liquid crystal components contacts with described sealant.
16. a method of making LCD, described method comprises:
A) provide display box with partition wall;
B) fill described display box with liquid crystal components; And
C) display box of filling is passed through in the sealant sealing that is used in the top original position sclerosis of described liquid crystal components.
17. method according to claim 16, wherein said sealant are by UV, the component of heat or moisture-curable forms.
18. being divided by the seal group that comprises thermoplasticity or thermoset precursors thing, method according to claim 16, wherein said sealant form.
19. method according to claim 16, wherein said sclerosis is by solvent evaporation, interfacial reaction, and moisture, heat, radiation or its make up to be finished.
20. method according to claim 19, wherein said sclerosis is finished by radiation.
21. LCD according to claim 16, wherein said sealant are carried out the original position sclerosis when described sealing component is arranged in the top of the liquid crystal components that is filled in described display box.
22. method according to claim 16, wherein said display box comprise the miniature cup array that is filled with liquid crystal components that one deck is above.
23. method according to claim 16 further comprises color filter is stacked or coat on the described display.
24. method according to claim 16, wherein said liquid crystal components are partially filled in each of described display box.
25. method according to claim 24, wherein said partially filled liquid crystal components contacts with described sealant.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/759,212 US6795138B2 (en) | 2001-01-11 | 2001-01-11 | Transmissive or reflective liquid crystal display and novel process for its manufacture |
| US09/759,212 | 2001-01-11 |
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| CNB011344121A Division CN1206564C (en) | 2001-01-11 | 2001-10-31 | Improved transmissive and reflective liquid crystal display and method thereof |
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| CNB2005100682213A Expired - Lifetime CN100543543C (en) | 2001-01-11 | 2001-10-31 | A kind of transmission-type of improvement or reflective liquid-crystal display and preparation method thereof |
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| EP (1) | EP1352289A2 (en) |
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- 2001-10-29 TW TW090126680A patent/TWI293701B/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2002056097A3 (en) | 2003-01-09 |
| TW200813528A (en) | 2008-03-16 |
| WO2002056097A2 (en) | 2002-07-18 |
| US6795138B2 (en) | 2004-09-21 |
| CN1363849A (en) | 2002-08-14 |
| MXPA03006176A (en) | 2004-03-10 |
| JP4278978B2 (en) | 2009-06-17 |
| KR20030075159A (en) | 2003-09-22 |
| JP2007233419A (en) | 2007-09-13 |
| CN1206564C (en) | 2005-06-15 |
| JP2004521377A (en) | 2004-07-15 |
| HK1047476A1 (en) | 2003-03-14 |
| TWI293701B (en) | 2008-02-21 |
| AU2002241837A1 (en) | 2002-07-24 |
| US20020126249A1 (en) | 2002-09-12 |
| KR100844305B1 (en) | 2008-07-07 |
| EP1352289A2 (en) | 2003-10-15 |
| US7095477B2 (en) | 2006-08-22 |
| CN1673833A (en) | 2005-09-28 |
| TWI304140B (en) | 2008-12-11 |
| US20040169813A1 (en) | 2004-09-02 |
| CA2434222A1 (en) | 2002-07-18 |
| HK1047476B (en) | 2005-12-09 |
| US6784953B2 (en) | 2004-08-31 |
| US20030169387A1 (en) | 2003-09-11 |
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